U.S. patent application number 16/375095 was filed with the patent office on 2020-10-08 for fine silver particle dispersion.
The applicant listed for this patent is E I DU PONT DE NEMOURS AND COMPANY. Invention is credited to Howard David Glicksman, Takashi Hinotsu, Dave Hui, Shingo Teragawa, Michael Stephen Wolfe, Haixin Yang.
Application Number | 20200317935 16/375095 |
Document ID | / |
Family ID | 1000004019985 |
Filed Date | 2020-10-08 |
United States Patent
Application |
20200317935 |
Kind Code |
A1 |
Hui; Dave ; et al. |
October 8, 2020 |
Fine Silver Particle Dispersion
Abstract
This disclosure relates to a conductive paste comprising a fine
silver particle dispersion and a glass frit, wherein the fine
silver particle dispersion comprising: (1) 65 to 95.4% by weight of
fine silver particles which have average primary particle diameter
of 10 to 190 nm and which comprise 25% by number or less of silver
particles having primary particle diameter of 100 nm or larger, (2)
4.5 to 34.5% by weight of a solvent, (3) 0.1 to 1.0% by weight of
ethyl cellulose having weight average molecular weight of 10,000 to
120,000. Also provided are: a method of manufacturing an
electrically conductive thick film comprising steps of: (a)
applying said fine silver particle dispersion on a substrate, and
(b) heating the applied fine silver particle dispersion at 80 to
1000 .degree. C.; and an electrical device comprising a conductive
thick film made with the foregoing paste.
Inventors: |
Hui; Dave; (Bristol South
Gloucestershire, GB) ; Wolfe; Michael Stephen;
(Wilmington, DE) ; Glicksman; Howard David;
(Durham, NC) ; Yang; Haixin; (Durham, NC) ;
Hinotsu; Takashi; (Tokyo, JP) ; Teragawa; Shingo;
(Tokyo, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
E I DU PONT DE NEMOURS AND COMPANY |
Wilmington |
DE |
US |
|
|
Family ID: |
1000004019985 |
Appl. No.: |
16/375095 |
Filed: |
April 4, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08K 9/04 20130101; C09D
5/24 20130101; C08K 3/40 20130101; C09D 101/28 20130101; C08K
2003/0806 20130101; C08K 2201/001 20130101; C08K 2201/003
20130101 |
International
Class: |
C09D 5/24 20060101
C09D005/24; C09D 101/28 20060101 C09D101/28 |
Claims
1. A conductive paste comprising a fine silver particle dispersion
and a glass frit, wherein the fine silver particle dispersion
comprises: (1) 65 to 95.4% by weight of fine silver particles which
have an average primary particle diameter of 10 to 190 nm and which
comprise 25% by number or less of silver particles having a primary
particle diameter of 100 nm or larger, (2) 4.5 to 34.5% by weight
of a solvent, and (3) 0.1 to 1.0% by weight of ethyl cellulose
having a weight average molecular weight of 10,000 to 120,000.
2. The conductive paste of claim 1, wherein the fine silver
particles are coated with an organic protective material.
3. The conductive paste of claim 2, wherein the organic protective
material is an amine with carbon number of from 8 to 12.
4. The conductive paste of claim 1, wherein a boiling point of the
solvent is 150 to 350.degree. C.
5. The conductive paste of claim 1, wherein the solvent is selected
from the group consisting of diethylene glycol monobutyl ether,
diethylene glycol dibutyl ether, diethylene glycol monobutyl ether
acetate, terpineol, and any mixture thereof.
6. The conductive paste of claim 1, wherein the ethyl cellulose has
a weight average molecular weight of 30,000 to 105,000.
7. The conductive paste of claim 1, wherein the ethyl cellulose has
a weight average molecular weight of 50,000 to 90,000.
8. The conductive paste of claim 1, wherein the fine silver
particle dispersion comprises 0.3 to 0.9% by weight of the ethyl
cellulose.
9. The conductive paste of claim 1, wherein the fine silver
particle dispersion comprises 0.6 to 0.9% by weight of the ethyl
cellulose.
10. The conductive paste of claim 1, wherein the fine silver
particles have an average primary particle diameter of 25 to 110
nm.
11. The conductive paste of claim 1, wherein the fine silver
particle dispersion comprises 70 to 87% by weight of the fine
silver particles.
12. The conductive paste of claim 1, wherein the fine silver
particles comprise 15% by number or less of silver particles having
a primary particle diameter of 100 nm or larger.
13. The conductive paste of claim 1, wherein an amount of a
substance having a weight average molecular weight of 150,000 or
more in the fine silver particle dispersion is 0.09% by weight or
less.
14. The conductive paste of claim 1, wherein the fine silver
particle dispersion comprises 11.1 to 31.5% by weight of the
solvent.
15. The conductive paste of claim 1, wherein an amount of a
substance having a weight average molecular weight of 150,000 or
more in the fine silver particle dispersion is 0.05% by weight or
less.
16. An electrical device comprising a conductive thick film made
with the conductive paste of claim 1.
17. The electrical device of claim 16, wherein the electrical
device is selected from the group consisting of a solar cell, an
LED, a display, a power module, a chip resistor, a chip conductor,
a filter, an ink-jet printer, an antenna, a wireless charger, a
capacitive sensor and a haptic device.
18. A method of manufacturing an electrically conductive thick film
comprising steps of: (a) applying a fine silver particle dispersion
on a substrate, wherein the fine silver particle dispersion
comprises, (i) 65 to 95.4% by weight of fine silver particles,
which have average primary particle diameter of 10 to 190 nm and
which comprise 25% by number or less of silver particles having
primary particle diameter of 100 nm or larger, (ii) 4.5 to 34.5% by
weight of a solvent; and (iii) 0.1 to 1.0% by weight of ethyl
cellulose having weight average molecular weight of 10,000 to
120,000; and (b) heating the applied fine silver particle
dispersion at 80 to 1000.degree. C.
19. The method of claim 18, wherein the fine silver particles are
coated with an organic protective material.
20. The method of claim 19, wherein the organic protective material
is an amine with carbon number of from 8 to 12.
21. The method of claim 18, wherein the ethyl cellulose has a
weight average molecular weight of 30,000 to 105,000.
22. The method of claim 18, wherein an amount of a substance having
a weight average molecular weight of 150,000 or more in the fine
silver particle dispersion is 0.05% by weight or less.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This subject matter of this application is related to that
of (i) an application entitled "FINE SILVER PARTICLE DISPERSION"
and bearing attorney docket number 185965 that is being filed
contemporaneously with this application; (ii) U.S. application Ser.
No. 15/724,378, filed on Oct. 4, 2017, and (iii) U.S. application
Ser. No. 15/724,392, filed on Oct. 4, 2017.
FIELD OF THE INVENTION
[0002] The present invention relates generally to a fine silver
particle dispersion. More specifically, the invention relates to a
fine silver particle dispersion used for forming an electrically
conductive thick film of electrical devices.
TECHNICAL BACKGROUND OF THE INVENTION
[0003] Fine silver particle dispersions that contain fine silver
particles dispersed in a solvent are used for forming an
electrically conductive thick film. The film can be used to form a
circuit, an electrode or an electrically conductive bonding
layer.
[0004] US20160297982 discloses a silver particle dispersion. The
silver particle dispersion contains fine silver particles (the
content of silver in the fine silver particle dispersing solution
is 30 to 90% by weight), which have primary particle diameter of 1
to 100 nm and which are coated with an amine having a carbon number
of 8 to 12, such as octylamine, serving as an organic protective
material; a polar solvent (5 to 70% by weight) having a boiling
point of 150 to 300.degree. C.; and an acrylic dispersing agent
(1.5 to 5% by weight with respect to the fine silver particles),
such as a dispersing agent of at least one of acrylic acid ester
and methacrylic acid ester.
SUMMARY OF THE INVENTION
[0005] An objective is to provide a fine silver particle dispersion
that has good storage stability of resistivity and that can be used
for forming an electrically conductive thick film with a good
surface smoothness and low resistivity.
[0006] An aspect relates to a fine silver particle dispersion
comprising: (1) 65 to 95.4% by weight of fine silver particles
which have an average primary particle diameter of 10 to 190 nm and
which comprise 25% by number or less of silver particles having a
primary particle diameter of 100 nm or larger, (2) 4.5 to 34.5% by
weight of a solvent, (3) 0.1 to 1.0% by weight of ethyl cellulose
having a weight average molecular weight of 10,000 to 120,000.
[0007] A fine silver particle dispersion that has good storage
stability of resistivity and that can be used for forming an
electrically conductive thick film with a good surface smoothness
and low resistivity can be provided by the present invention.
[0008] Further aspects relate to a conductive paste comprising the
foregoing fine silver particle dispersion and a glass frit, an
electrical device comprising a conductive thick film made with such
paste, and a method of manufacturing an electrically conductive
thick film using such paste.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Fine Silver Particle Dispersion
[0009] A fine silver particle dispersion comprises fine silver
particles, a solvent and ethyl cellulose having a specific weight
average molecular weight.
Fine Silver Particles
[0010] The fine silver particles have an average primary particle
diameter of 10 to 190 nm and comprise 25% by number or less of
silver particles having a primary particle diameter of 100 nm or
larger. The fine silver particles with the average primary particle
diameter impart low resistivity to an electrically conductive thick
film formed from the fine silver particle dispersion. Further, when
number percentage of silver particles with a primary particle
diameter of 100 nm or larger is more than 25%, resistivity of the
electrically conductive thick film formed from the fine silver
particle dispersion is high. Also, the fine silver particles which
have the above small average primary particle diameter and have
small number of medium to large size particles (100 nm or larger)
are suitable for sintering at a low temperature. In some
embodiments, the fine silver particles in the dispersion can
comprise 15% by number or less of silver particles having a primary
particle diameter of 100 nm or larger, and in some embodiments can
comprise 10% by number or less of silver particles having a primary
particle diameter of 100 nm or larger.
[0011] The average primary particle diameter of the fine silver
particles is 10 to 150 nm in an embodiment, 25 to 110 nm in another
embodiment, 30 to 85 nm in another embodiment, 50 to 70 nm in
another embodiment. The primary particle diameter is measured by
analyzing an image picture with an image analysis software
(A-zo-kun.RTM., Asahi Kasei Engineering Corporation). The image
picture can be taken by a scanning electron microscope (SEM)
(S-4700, Hitachi High-Technologies Corporation) or a transmission
electron microscope (TEM) (JEM-1011, Japan Electron Optics
Laboratory Ltd.). The average primary particle diameter of the fine
silver particles is calculated as an average value of primary
particle diameters of more than 100 arbitrary fine silver particles
in the image picture.
[0012] The fine silver particles are coated with an organic
protective material in an embodiment. The organic protective
material is an amine with carbon number of from 8 to 12 in an
embodiment. The amine can be selected from the group consisting of
octylamine, nonylamine, decylamine, dodecylamine and a combination
thereof in an embodiment. The amine can comprise octylamine in
another embodiment. By coating fine silver particles with the
amine, it is possible to suitably hold the distance between
adjacent fine silver particles so as to prevent the sintering of
the fine silver particles with each other.
[0013] The particle diameter (D50) of the fine silver particles is
50 to 300 nm in an embodiment, 55 to 250 nm in another embodiment,
75 to 210 nm in another embodiment, 95 to 180 nm in another
embodiment. The particle diameter (D50) of the fine silver
particles after dispersion in solvent is the 50.sub.th percentile
diameter in a volume-based particle diameter distribution that can
be measured by Dynamic Light Scattering (Nanotrac Wave-EX150,
NIKKISO CO., LTD.).
[0014] Content of the fine silver particles is 65 to 95.4% by
weight, 65 to 90% by weight in an embodiment, 68 to 88% by weight
in another embodiment, 70 to 87% by weight in another embodiment,
based on the weight of the fine silver particle dispersion.
Solvent
[0015] The fine silver particles are dispersed in a solvent. In an
embodiment, a boiling point of the solvent is 150 to 350.degree.
C., 175 to 310.degree. C. in another embodiment, 195 to 260.degree.
C. in another embodiment.
[0016] The solvent is selected from the group consisting of
diethylene glycol monobutyl ether, diethylene glycol dibutyl ether,
diethylene glycol monobutyl ether acetate, terpineol, and any
mixture thereof in an embodiment.
[0017] Content of the solvent is 4.5 to 34.5% by weight, 9.05 to
34.5% by weight in an embodiment, 11.1 to 31.5% by weight in
another embodiment, 12.15 to 29.5% by weight in another embodiment,
based on the weight of the fine silver particle dispersion.
Ethyl Cellulose
[0018] The fine silver particle dispersion comprises 0.1 to 1.0% by
weight of ethyl cellulose. A weight average molecular weight of the
ethyl cellulose is 10,000 to 120,000.
[0019] Without being bound by any theory, it is believed that
incorporating certain combinations of ethyl cellulose and solvent
in a silver particle dispersion enhances the dispersion
stability.
[0020] The weight average molecular weight of the ethyl cellulose
is 10,000 to 120,000, which enables the fine silver particle
dispersion to form an electrically conductive thick film with a
good surface smoothness and low resistivity and which imparts good
storage stability of resistivity to the dispersion. The weight
average molecular weight is 23,000 to 110,000 in an embodiment,
30,000 to 105,000 in another embodiment, 50,000 to 90,000 in
another embodiment, and 65,000 to 85,000 in another embodiment.
[0021] Ethyl cellulose is commercially available from Dow Chemical
Company under the tradename ETHOCEL.RTM.. Exemplary grades useful
in the present dispersion include ones available as ETHOCEL.RTM.
STD 4 (Mw: 44046), STD 7 (Mw: 55205), STD 10 (Mw: 77180), STD 14,
and STD 20 (Mw: 105059).
[0022] The content of ethyl cellulose can be 0.1 to 1.0% by weight
based on the weight of the fine silver particle dispersion. When
the content is lower than 0.1 by weight, it is difficult to prepare
a dispersion. When the content is larger than 1.0% by weight, low
resistivity cannot be obtained regarding an electrically conductive
thick film formed from the fine silver particle dispersion. The
content of ethyl cellulose is 0.2 to 0.95% by weight in an
embodiment, 0.3 to 0.9% by weight in another embodiment, 0.5 to
0.85% by weight in another embodiment, and 0.6 to 0.9% by weight in
another embodiment.
Substance with a Large Molecular Weight
[0023] In some aspects, the fine silver particle dispersion of the
present invention can include substantially no substance with a
large molecular weight. Specifically, content of a substance having
a weight average molecular weight of 150,000 or more in the fine
silver particle dispersion is 0.25% by weight or less, 0.09% by
weight or less, 0.05% by weight or less, 0.03% by weight or less in
an embodiment, or 0.02% by weight or less in another embodiment. It
is presumed that this kind of large molecule inhibits sintering of
the fine silver particles, leading to a high resistivity of the
electrically conductive thick film. Further, the substance may
lower the surface smoothness of the electrically conductive thick
film. As an example, this large molecular weight substance can be a
polymer or a combination of polymers, including other ethyl
cellulose polymers.
[0024] The fine silver particle dispersion comprises no glass frit
in an embodiment.
How to Make Fine Silver Particle Dispersion
[0025] The fine silver particle dispersion can be produced by a
method comprising the steps of: (i) producing fine silver particles
by reducing a silver compound in the presence of an organic
protective material such as an amine and a reducing agent in water
to get a water slurry containing fine silver particles coated with
the organic protective material; (ii) removing some of the liquid
from the aqueous slurry after decantation to get the fine silver
particle; and (iii) adding the concentrated fine silver particle
slurry to an ethyl cellulose solution containing at least a solvent
and ethyl cellulose. The fine silver particle dispersion can be
further put in a nitrogen atmosphere for 12 hours or more to remove
the moisture content therein in an embodiment. The temperature of
the atmosphere can be room temperature in an embodiment. The
temperature of the atmosphere can be heated to between 80 and
100.degree. C. in another embodiment. The moisture can be removed
by heating in another embodiment. A vacuum condition also can be
available to remove the moisture in another embodiment.
[0026] The silver compound is a silver salt or a silver oxide in an
embodiment. The silver salt is silver nitrate (AgNO.sub.3) in
another embodiment. The silver compound is added so that the
concentration of silver ions in the water is in the range of 0.01
to 1.0 mol/L in an embodiment, 0.03 to 0.2 mol/L in another
embodiment.
[0027] The molar ratio of the organic protective material to silver
of the silver compound (organic protective material/Ag) is 0.05 to
6 in an embodiment.
[0028] The reduction treatment of the silver compound is carried
out at 60.degree. C. or lower in an embodiment, 10 to 50.degree. C.
in another embodiment. With such temperature, each of the fine
silver particles can be sufficiently coated with the organic
protective material so as not to aggregate. The reaction time in
the reduction treatment is 30 minutes or shorter in an embodiment,
10 minutes or shorter in another embodiment.
[0029] Any reducing agent can be used as long as it reduces silver.
The reducing agent is a basic reducing agent in an embodiment. The
reducing agent is hydrazine or sodium borohydride (NaBH.sub.4) in
another embodiment. The equivalent ratio of the reducing agent to
silver of the silver compound (reducing agent/Ag) is 0.4 to 8.0 in
an embodiment.
[0030] The fine silver particle dispersion can be further kneaded
and degassed by a three-roll mill, a bead mill, a wet jet mill, or
an ultrasonic homogenizer in another embodiment.
[0031] Viscosity of the fine silver particle dispersion is 30 to
350 Pas in an embodiment, 40 to 300 Pas in another embodiment, 45
to 280 Pas in another embodiment, 50 to 220 Pas in another
embodiment at shear rate 15.7 5.sup.-1 at 25.degree. C. The
viscosity of the fine silver particle dispersion can be measured by
a viscosity measuring apparatus (HAAKE RheoStress 600, Thermo
Fisher Scientific Inc.) with C35/2 cone and plate at shear rate
15.7 5.sup.-1 at 25.degree. C.
Use of the Fine Silver Particle Dispersion
[0032] An electrically conductive thick film can be formed by using
the fine silver particle dispersion. The electrically conductive
thick film may be used to form a circuit, an electrode or an
electrically conductive bonding layer in an embodiment.
[0033] A method of manufacturing an electrically conductive thick
film comprising steps of: (a) applying a fine silver particle
dispersion on a substrate, wherein the fine silver particle
dispersion comprises, (1) 65 to 95.4% by weight of fine silver
particles which have an average primary particle diameter of 10 to
190 nm and which comprise 25% by number or less of silver particles
having a primary particle diameter of 100 nm or larger, (2) 4.5 to
34.5% by weight of a solvent, (3) 0.1 to 1.0% by weight of ethyl
cellulose having a weight average molecular weight of 10,000 to
120,000; and heating the applied fine silver particle dispersion at
80 to 1000.degree. C.
[0034] There is no restriction on the substrate. The substrate can
be a polymer film, a glass substrate, a ceramic substrate, a
semiconductor substrate or a metal substrate in an embodiment.
[0035] The fine silver particle dispersion is applied by screen
printing, inkjet printing, gravure printing, stencil printing, spin
coating, blade coating or nozzle discharge in an embodiment. The
fine silver particle dispersion is screen printed on a substrate in
another embodiment.
[0036] The heating temperature is 900.degree. C. or lower in an
embodiment, 820.degree. C. or lower in another embodiment,
700.degree. C. or lower in another embodiment, 550.degree. C. or
lower in another embodiment, 410.degree. C. or lower in another
embodiment, 320.degree. C. or lower in another embodiment,
260.degree. C. or lower in another embodiment, 160.degree. C. or
lower in another embodiment. A heating temperature of 160.degree.
C. or lower is suitable for a polymer film substrate which may be
susceptible to heat damage. The heating temperature is 70.degree.
C. or higher in an embodiment, 100.degree. C. or higher in another
embodiment, 120.degree. C. or higher in another embodiment. The
heating time is 10 to 200 minutes in an embodiment, 15 to 160
minutes in another embodiment, 20 to 120 minutes in another
embodiment, 25 to 95 minutes in another embodiment, 25 to 80
minutes in another embodiment. The fine silver particles can be
sufficiently sintered during heating with the temperature and time
described above.
[0037] The electrically conductive thick film is 1 to 50 .mu.m
thick in an embodiment, 2 to 45 .mu.m thick in another embodiment,
3 to 40 .mu.m thick in another embodiment, 4 to 35 .mu.m thick in
another embodiment, 5 to 30 .mu.m thick in another embodiment.
[0038] An electrical device comprises one or more electrically
conductive thick film manufactured using the fine silver particle
dispersion of the present invention. The electrical device is
selected from the group consisting of a solar cell, an LED, a
display, a power module, a chip resistor, a chip conductor, a
filter, an antenna, a wireless charger, a capacitive sensor and a
haptic device in an embodiment.
Electrically Conductive Paste
[0039] The fine silver particle dispersion can be used to form an
electrically conductive paste in an embodiment. The electrically
conductive paste comprises a fine silver particle dispersion and a
glass frit in an embodiment. The glass frit could promote sintering
of the fine silver particle and adherence to the substrate during
firing.
[0040] Particle diameter (D50) of the glass frit can be 0.1 to 7
.mu.m in an embodiment, 0.3 to 5 .mu.m in another embodiment, 0.4
to 3 .mu.m in another embodiment, 0.5 to 1 .mu.m in another
embodiment. The particle diameter (D50) is obtained as described
above with regard to the fine silver particles.
[0041] In an embodiment, softening point of the glass frit can be
310 to 600.degree. C., in another embodiment 350 to 500.degree. C.,
in another embodiment, 410 to 460.degree. C. When the softening
point is in the range, the glass frit can melt properly to obtain
the effects mentioned above. Here, the "softening point" is the
softening point obtained by the fiber elongation method of ASTM
C338-57.
[0042] The chemical composition of the glass frit here is not
limited. Any glass frits suitable for use in the electrically
conductive paste is acceptable. The glass frit comprises a lead
silicate glass frit, a lead borosilicate glass frit, a lead
tellurium glass frit, a zinc borosilicate glass frit, a lead-free
bismuth boron glass frit or any mixture thereof in an
embodiment.
[0043] The amount of the glass frit can be determined based on the
amount of the fine silver particles. The weight ratio of the fine
silver particles and the glass frit (fine silver-particles:
glass-frit) can be 10:1 to 100:1 in an embodiment, 25:1 to 80:1 in
another embodiment, 30:1 to 68:1 in another embodiment, 42:1 to
53:1 in another embodiment. With such amount of the glass frit,
sintering of the fine silver particles and adhesion between an
electrically conductive thick film and a substrate can be
sufficient.
[0044] Content of the glass frit is 0.5 to 8 parts by weight in an
embodiment, 0.8 to 6 parts by weight in another embodiment, 1.0 to
3 parts by weight in another embodiment based on 100 parts by
weight of the electrically conductive paste.
[0045] The electrically conductive paste comprises the fine silver
particle dispersion and an additional silver powder in another
embodiment. The additional silver powder could increase electrical
conductivity of a formed electrically conductive thick film.
[0046] The particle diameter (D50) of the additional silver powder
is 0.4 to 10 .mu.m in an embodiment, 0.6 to 8 .mu.m in another
embodiment, 0.8 to 5 .mu.m in another embodiment, 1 to 3 .mu.m in
another embodiment.
[0047] The particle diameter (D50) of the additional silver powder
is determined from a measured distribution of the particle
diameters by using a laser diffraction scattering method. Microtrac
model X-100 is an example of a commercially-available device useful
in carrying out particle size distribution measurements.
[0048] The additional silver powder is flaky or spherical in shape
in an embodiment.
[0049] Content of the additional silver powder is 10 to 60 parts by
weight in an embodiment, 18 to 53 parts by weight in another
embodiment, 26 to 49 parts by weight in another embodiment based on
100 parts by weight of the electrically conductive paste.
[0050] The electrically conductive paste comprises the fine silver
particle dispersion, the glass frit and the additional silver
powder in another embodiment.
Use of the Electrically Conductive Paste
[0051] An electrically conductive thick film can be formed by using
the electrically conductive paste. The electrically conductive
thick film may form a circuit, an electrode or an electrically
conductive bonding layer as described above in an embodiment.
[0052] A method of manufacturing an electrically conductive thick
film comprises the steps of: (a) applying an electrically
conductive paste on a substrate, wherein the electrically
conductive paste comprises a fine silver particle dispersion and a
glass frit, wherein the fine silver particle dispersion comprises
(1) 65 to 95.4% by weight of fine silver particles which have an
average primary particle diameter of 10 to 190 nm and which
comprise 25% by number or less of silver particles having a primary
particle diameter of 100 nm or larger, (2) 4.5 to 34.5% by weight
of a solvent, (3) 0.1 to 1.0% by weight of ethyl cellulose having a
weight average molecular weight of 10,000 to 120,000; and (b)
firing the applied electrically conductive paste at 600 to
1000.degree. C. The electrically conductive paste used in the
method of manufacturing an electrically conductive thick film can
comprise an additional silver powder instead of or together with
the glass frit in another embodiment.
[0053] The substrate is a glass substrate, a ceramic substrate or a
semiconductor substrate in an embodiment. The electrically
conductive paste is applied by screen printing, inkjet printing,
gravure printing, stencil printing, spin coating, blade coating or
nozzle discharge in an embodiment. The electrically conductive
paste is screen printed on a substrate in another embodiment.
[0054] The firing temperature is 920.degree. C. or lower in an
embodiment, 880.degree. C. or lower in another embodiment,
830.degree. C. or lower in another embodiment, 780.degree. C. or
lower in another embodiment. The firing temperature is 650.degree.
C. or higher in an embodiment, 700.degree. C. or higher in another
embodiment. The firing time is 5 seconds or longer in an
embodiment, 30 seconds or longer in another embodiment, 1 minute or
longer in another embodiment, 7 minutes or longer in another
embodiment, 15 minutes or longer in another embodiment, 25 minutes
or longer in another embodiment. The firing time is 200 minutes or
shorter in an embodiment, 160 minutes or shorter in another
embodiment, 110 minutes or shorter in another embodiment, 95
minutes or shorter in another embodiment, 75 minutes or shorter in
another embodiment.
EXAMPLES
Examples 1 and 2
[0055] Pure water 125.7 kg as a reaction medium was put in a 200 L
of reactor and the temperature was adjusted to 40.degree. C.
Octylamine as an organic protective material 2431.2 g and 80%
hydrazine hydrate as a reducing agent 230.7 g were added to the
reactor. The molar ratio of octylamine to silver (octylamine/Ag)
was 2. The equivalent ratio of hydrazine hydrate to silver
(hydrazine hydrate/Ag) was 2.0. The mixture in the reactor was
stirred at 158 rpm with a stirring rod having impellers. Nitrogen
gas as an inert gas was blown into the reactor at a flow rate of 20
L/min. An aqueous solution of 1253.6 g of a silver nitrate (Toyo
Kagaku Inc.) dispersed in 6702.6 g of pure water was added to the
reactor. A water dispersion containing fine silver particles coated
with octylamine was obtained by stirring the mixture at 158 rpm in
the reactor for another two minutes.
[0056] To measure the primary particle diameter of the fine silver
particles made above, a few drops of the water dispersion were
placed on a glass substrate. The water dispersion on the glass
substrate was dried at 60.degree. C. so that the fine silver
particles remained. An image picture of the fine silver particles
remained on the glass substrate was taken by a scanning electron
microscope (SEM) (S-4700 produced by Hitachi High-Technologies
Corporation) at 50,000-times magnification and analyzed by image
analysis software (A-zo-kun.RTM., Asahi Kasei Engineering
Corporation). The diameters of more than 100 primary particles were
measured and average primary particle diameter thereof was
obtained. SEM images with aggregated particles and irregular-shaped
particles were determined to be immeasurable.
[0057] The measured average primary particle diameter was 57.8 nm.
The dispersion comprised 5% by number or less of silver particles
having primary particle diameter of 100 nm or larger.
[0058] The wet fine silver particles in the water dispersion were
collected by decantation where most of the liquid was removed after
fine silver particles sedimentation.
[0059] Ethyl cellulose (ETHOCEL.TM. STD 10, Mw: 77,180, Tg:
130.degree. C., Dow Chemical Company) was dissolved in diethylene
glycol monobutyl ether (DGBE) and stirred for 6 hours at 60.degree.
C. by a magnetic stirrer. The stirring speed was 1000 rpm.
[0060] DGBE was a polar solvent having a boiling point of
230.degree. C. and a solubility parameter value of 9.5.
[0061] Wet fine silver particles obtained above were dispersed in
the ETHOCEL.TM. STD 10 solution. The fine silver particle
dispersion was obtained by drying the mixture of the wet fine
silver particles and the resin solution at 30.degree. C. under
vacuum for 8 hours to remove the water therein. The amount of
components of the fine silver particle dispersion is shown in Table
1.
[0062] The secondary particle diameters (D50) of the fine silver
particle dispersions of Example 1 and Example 2 were measured by
Dynamic Light Scattering (Nanotrac Wave-EX150, NIKKISO CO., LTD.).
A 10,000-fold dilution of the fine silver particle dispersion was
made by adding DGBE to the fine silver particle dispersion followed
by sonication with an ultrasonic bath. The 10,000-fold dilution of
the fine silver particle dispersion was used for the particle
diameter (D50) measurement. The results are shown in Table 1.
TABLE-US-00001 TABLE 1 (wt. %) Example 1 Example 2 Silver particles
80.9 79.9 ETHOCEL .TM. STD 10 0.7 0.9 DGBE solvent 18.4 19.2
Average primary particle diameter 57.8 nm D50 134.7 nm 157.5 nm
[0063] The fine silver particle dispersion of Example 1 was coated
on a glass substrate and fired at 130.degree. C..times.30 min by a
hot-air dryer to prepare an electrically conductive thick film.
[0064] Thickness and surface roughness of the fired film were
measured by a thickness measuring apparatus (SURFCOM 1500DX, Toyo
Precision Parts MFG Co., Ltd.). Operation range of the measurement
was 10 mm and scanning speed was 0.6 mm/s. Surface roughness of the
fired film was obtained as Ra value by this measurement. Volume
resistivity of the fired film was measured by a surface resistance
measuring apparatus (MCP-T610, Mitsubishi Chemical Analytech). The
results are shown in Table 2.
TABLE-US-00002 TABLE 2 Example 1 Thickness 8.55 .mu.m Surface
roughness 0.082 .mu.m Volume resistivity 6.40 .mu..OMEGA. cm
[0065] An electrically conductive thick film was formed from the
fine silver particle dispersion of Example 2 immediately after
preparation of the dispersion and volume resistivity was evaluated
in similar manner to Example 1 except for firing the coated
dispersion for 60 min.
[0066] Separately, a part of the dispersion was stored at
25.degree. C. for 3 months and volume resistivity was evaluated in
the same manner (130.degree. C..times.60min). The results are shown
in Table 3.
TABLE-US-00003 TABLE 3 Example 2 Volume resistivity 3.8 .mu..OMEGA.
cm Volume resistivity after 3 month storage 3.9 .mu..OMEGA. cm
Example 3
[0067] It was attempted to prepare a fine silver particle
dispersion in the same manner as in Example 1 except that
ETHOCEL.TM. STD 10 was not added. As a result, composition as a
dispersion where the silver particles were dispersed in the solvent
was not obtained.
Example 4
[0068] A fine silver particle dispersion was prepared in the same
manner as in Example 1 except that the composition of the
dispersion was changed as shown in the table 4.
TABLE-US-00004 TABLE 4 (wt. %) Example 4 Silver particles 86.2
M1400 2.6 DGBE solvent 11.2
[0069] M1400 is an acrylic resin available from SEKISUI CHEMICAL
CO., LTD. whose Mw is about 25,000.
[0070] Storage stability was evaluated regarding the fine silver
particle dispersion obtained above in the same manner as in Example
2. The results are shown in Table 5.
TABLE-US-00005 TABLE 5 Example 2 Example 4 Volume resistivity 3.8
.mu..OMEGA. cm 12.9 .mu..OMEGA. cm Volume resistivity after 3 month
storage 3.9 .mu..OMEGA. cm Unmeasurably high
[0071] It is presumed that the storage stability is enhanced by
increasing the resin (ETHOCEL.TM. STD 10 or M1400) content in the
dispersion because the resin inhibits collision of particles. The
dispersion used in Example 4 contained a larger amount of resin
(M1400) than Example 2. However, its storage stability was
poor.
Example 5
[0072] Polyvinyl alcohol (PVA) (Mw: about 90,000) was used instead
of ETHOCEL.TM. STD 10 in Example 1. It was attempted to disperse
the PVA and the silver particles in the solvent (DGBE). However,
fine silver particle dispersion was not obtained.
Example 6
[0073] A fine silver particle dispersion was prepared in the same
manner as in Example 1 except that, as ethyl cellulose, 0.6% by
weight of ETHOCEL.TM. STD 10 and 0.1% by weight of ETHOCEL.TM. STD
100 (Mw: about 180,000) were used.
[0074] Volume resistivity and surface roughness of an electrically
conductive thick film were evaluated in the same manner as in
Example 1 (130.degree. C..times.30min). The results are shown in
Table 6.
TABLE-US-00006 TABLE 6 Example 6 Thickness 9.30 .mu.m Surface
roughness 0.371 .mu.m Volume resistivity 38.1 .mu..OMEGA. cm
[0075] In the results, surface roughness and volume resistivity
were inferior to Example 1.
Example 7
[0076] It was attempted to prepare a fine silver particle
dispersion in the same manner as in Example 1 except that
ETHOCEL.TM. STD 100 was used instead of ETHOCEL.TM. STD 10. As a
result, composition as a dispersion where the silver particles were
dispersed in the solvent was not obtained (the silver particles and
the solvent were clearly separated).
Example 8
[0077] A fine silver particle dispersion was prepared in the same
manner as in Example 1 except that the composition of the
dispersion was changed as shown in the table 7, and volume
resistivity of an electrically conductive thick film was evaluated
in the same manner as in Example 1.
TABLE-US-00007 TABLE 7 (wt. %) Example 8 Silver particles 79.9
ETHOCEL .TM. STD 10 1.2 DGBE solvent 18.9 Volume resistivity 48.0
.mu..OMEGA. cm
[0078] In the result, volume resistivity was inferior to Example
1.
* * * * *